US3884688A

US3884688A - Photosensitive element employing a vitreous bismuth-selenium film

Info

Publication number: US3884688A
Authority: US
Inventors: John C Schottmiller; Francis W Ryan; Charles Wood
Original assignee: Xerox Corp
Current assignee: Xerox Corp
Priority date: 1966-05-16
Filing date: 1973-01-05
Publication date: 1975-05-20
Anticipated expiration: 1992-05-20
Also published as: BE721965A; FR95985E; GB1250176A; US3874917A; US3887368A; NL6814501A; US3909458A; US3627573A; GB1251630A; DE1801636A1; CH517359A

Abstract

This invention relates to a vitreous semiconductor comprising at least one metal and at least one non-metal which is solid at room temperature, the semiconductor having at least 0.5 atomic percent metal and a greater than stoichiometric percentage of non-metal. The invention also relates to a method for producing such semiconductors by co-evaporating the metal and the non-metal and simultaneously quenching said metal and said non-metal onto a substrate held at a temperature below the condensation point of either component.

Description

United States Patent Schottmiller et al.

1111 3,884,688 1*May 20, 1975 PHOTOSENSITIVE ELEMENT EMPLOYING A VITREOUS BlSMUTH-SELENIUM FILM Inventors: John C. Schottmiller; Francis W.

Ryan, both of Penficld, N.Y,; Charles Wood. Sycamore, Ill.

Assignee: Xerox Corporation, Stamford,

Conn.

Notice: The portion of the term of this patent subsequent to Dec. 14, 1988, has been disclaimed.

Filed: Jan. 5, 1973 Appl. No.: 321,194

Related 1.1.8. Application Data Continuation-impart of Ser. No. 798,750, Feb, 12, 1969, abandoned, which is a continuation-impart of Ser, No. 674,267, Oct. 10, 1967, Pat, No. 3,627,573, which is a continuation-in-part of Ser. No 550,225, May 16, 1966, abandoned.

us. 01 915/15; 117/106 R; 117/201;

252/501; 313/385 1111. c1 G03g 5/04 Field 01 Search 96/1 .5; 252/501 References Cited UNITED STATES PATENTS 4/1967 Baldwin 252/501 X 2,868,736 1/1959 Weinreich 252/501 2,946,682 7/1960 Lauriello 1 1 96/1 R 2,959,481 11/1960 Kucera 96/1 R 2,962,376 11/1960 Schaffert 96/1 R 3.025160 3/1962 Bunge et a1 96/] R 3,041.166 6/1962 Bardeen 96/1 R 3,077,386 2/1963 Blakney ct a1. 1 .1 96/1 .5 3,345,161 10/1967 Mammino et a1 ,1 96/17 3,464,820 9/1969 Michalchik 96/118 3,627,573 12/1971 Schottmiller et al. 252/501 X Primary ExaminerNorman G, Torchin Assistant Examiner-John R. Miller [57] ABSTRACT This invention relates to a vitreous semiconductor comprising at least one metal and at least one r10nmetal which is solid at room temperature, the semiconductor having at least 0.5 atomic percent metal and a greater than stoichiometric percentage of nonmetal. The invention also relates to a method for producing such semiconductors by co-evaporating the metal and the non-metal and simultaneously quenching said metal and said non-metal onto a substrate held at a temperature below the condensation point of either component.

2 Claims, 4 Drawing Figures PATENTEU HAY 2 O [975 0.2 xsnosna mc GAIN 0| 3884.688 sum 30F 53 SELENIUM 2.0 I. Hi 4000 N Ll'l. Bl

sewsmvny' NEH x :0

WAVELENGTH (MICRONSI FIG. 3

PLATE SENSITIVlTY VS. COMPOSITION AT. /o Bl FIG. 4

W. 2 5% 4% 7% 8% IO% PHOTOSENSITIVE ELEMENT EMPLOYING A VITREOUS BISMUTI-l-SELENIUM FILM BACKGROUND OF THE INVENTION This application is a continuation-in-part of copending application Ser. No. 798,750, filed Feb. l2, I969, now adandoned, which is a continuation-in-part of application Ser. No. 674,267, now US. Pat. 3,627,573, filed Oct. 10, 1967, which is a continuation-in-part of application Ser. No. 550,225, filed May l6, I966, now abandoned, in the names of John Schottmiller, Francis Ryan and Charles Wood.

This invention relates to semiconductors or semiinsulators and in particular to a system utilizing new viteous semiconductors.

Two common semiconductors are highly purified silicon and germanium with slight traces (parts per million or billon) of selected impurities and/or crystal imperfections being present to modify or change the semiconductor properties.

These impurities cause either loosely bound electrons that can move or carry some current or the impurities remove electrons from their normal place in the lattice and so form a hole which can be filled by an adjacent electron whose movement creates a new hole which in turn is filled. The resulting movement of the hole is equivalent of electrical conduction in a direction opposite to that occurring when electrons move. Some of the more important semiconductor materials include silicon, germanium, selenium, cuprous oxide (Cu O), lead sulfide, silicon carbide, lead telluride, and other compounds. Typical semiconductor applications are for use in rectifiers, modulators, detectors, thermistors, photocells, transistors, and electrical circuits.

As shown above, it can be seen that semiconductors may be made up of single elements or may consist of various compounds exhibiting semiconductive properties.

The preparation of known semiconductor involve of necessity, carefully controlled processing steps such as special melt techniques in crystal growth, epitaxial deposition, involved doping techniques, etc. Such highly controlled processes add to the cost of the final product. There is, therefore, an ever present need for new semiconductor materials which yield a wider range of desirable electrical properties and yet may be simply and economically manufactured.

OBJECTS OF THE INVENTION It is, therefore, an object of this invention to provide a new class of semiconductors which overcome the above noted disadvantages.

It is another object of this invention to provide an improved process for producing thin layers of materials having improved electrical characteristics.

It is further object of this invention to provide an improved system for producing thin films of materials having improved electrical characteristics.

It is yet another object of this invention to provide a new class of vitreous semiconductors having desirable photoconductive properties.

It is another object of this invention to provide a new class of vitreous semiconductors having enhanced electrical characteristics.

It is a further object of this invention to provide a bismuth-selenium semiconductor having enhanced electrical characteristics.

SUMMARY OF THE INVENTION The foregoing objects and others are accomplished in accordance with the present invention by providing a method of forming new vitreous semiconductors having a wide range of compositions by co-evaporating at least one metal and at least one non-metal onto a substrate held at a temperature below the condensation point of either component. This substrate temperature will be substantially lower than either source temperature. By quenching the vapor of the components onto such a substrate, the different atoms are randomly mixed to form a continuous homogeneous noncrystalline film on said substrate, said film normally having greater than stoichiometric proportions of the non-metal component. The present invention is in contrast to Cameron (U.S. Pat. No. 2,932,599) who discloses a vapor quenching process in which the substrate is maintained at a temperature above the condensation point of the non-metal. Cameron, therefore, cannot produce semiconductive materials having a greater than stoichiometric amount of the non-metal. Cameron characterizes his material as a reaction product and a compound thereby supporting the view that semiconductive materials having greater than stoichiometric proportions of non-metal are not produced.

The materials of this invention can best be described as vitreous semiconductors or semi-insulators. These materials possess electrical properties different from the components taken separately, or combined in stoichiometric amounts. X-ray diffraction patterns of these materials are of the so-called vitreous or noncrystalline type. These vitreous semiconductors may be described as thermodynamically metastable, although they possess a high degree of phenomenological stability and retain their structure at relatively high temperatures. In some instances, the crystallization temperature of these vitreous semiconductors is higher than either component alone.

This new class of semiconductors comprises elements selected from at least one solid or liquid metal and at least one solid non-metal. Typical metals include cadmium, zinc, gallium, lead, thallium, neodymium, copper, silver, manganese, aluminum, bismuth, indium and antimony. Typical non-metals include selenium, boron, arsenic, carbon, phosphorus, sulphur and tellurium.

These films may be formed in any convenient thickness. Although thicknesses of several hundred angstroms may be formed, films ranging from about 1,000 up to 200 microns and higher, are most suitable for semiconductor applications.

BRIEF DESRIPTION OF THE DRAWINGS The advantages of this method will become apparent upon consideration of the following disclosure of the invention, especially when taken in conjunction with the accompanying drawings wherein:

FIG. 1 illustrates one embodiment of an apparatus for preparing thin films of vitreous semiconductors in accordance with this invention.

FIG. 2 illustrates a second embodiment of an apparatus for preparing thin films of vitreous semiconductors in accordance with this invention.

FIG. 3 graphically illustrates xerographic gain which is plotted as a function of wavelength for bismuthselenium films.

FIG. 4 graphically illustrates sensitivity plotted as a function of composition for bismuth-selenium films.

in FIG. 1, bell jar rests on support plate 11 containing vacuum line 12 and control valve 13. Resistance heating circuits l4 and 15 are employed to heat evaporation crucibles l6 and 17 containing

evaporation samples

18 and 19, respectively. A support 20, containing a water cooled base 21, is provided with water cooling means 22. The substrate 23, which is to be coated, is supported on the water cooled base 21. An aluminum mask 24, is hinged to base 21, and is adapted to overlay substrate 23 (as shown in dotted lines) to effectively mask the substrate until

evaporation samples

18 and 19 are heated to a suitable temperature.

The metal and non-metal are each placed in separate inert crucibles such as quartz or tantalum. In controlling the evaporation of the components, it is generally desirable to maintain the temperature of said components at between their melting point and boiling point. Thus, for example, in forming a cadmium-selenium amorphous film, containing about 20 percent cadmium and 80 percent selenium,'a temperature of about 217C for selenium and about 322C for the cadmium was found sufficient. To increase the amount of selenium in the film, the temperature of the cadmium container lowered. To increase the amount of cadmium in the film, the above temperature changes would be reversed. Where a very slow rate of evaporation is desired, the evaporation temperature of one or both components may be maintained at a temperature below their melting point.

The vacuum chamber is maintained at a vacuum of about 2 X 10" to 2 X 10' Torr, although vacua above and below this range can also be used satisfactorily. Under the above conditions, a film thickness of about 5 to 30 microns is obtained when evaporation is continued for a time ranging from about 1 to 3 hours at a vacuum of about 2 X 10 Torr. It can be seen that the amount of a particular component in the vitreous film is primarily dependent upon the amount of metal or non-metal evaporated which is source temperature dependent. lt should be noted that the vitreous film may also be formed under non-vacuum conditions such as by vapor transport or sputtering.

The vitreous semiconductor films may be formed on any suitable substrate whether it be conductive or insulating. Typical conductive substrates are brass, aluminum, stainless steel, conductively coated glass or plastic, etc. A particularly satisfactory conductive substrate comprise a partially transparent tin oxide coated glass sold under the tradename NESA glass and available from the Pittsburgh Plate Glass Company. Typical insulators are quartz, Pyrex, mica, polyethylene, etc.

in FIG. 2 a bell jar or vacuum chamber 30 rests on support plate 31 and contains a vacuum line 32 and control valve 33. A resistance heating circuit 34 is employed to heat crucible 35 which is supported near the bottom of the bell jar. A special mechanism designed for delivery of a premixed alloy powder comprises a chute 36 having a water cooled jacket 37 connected to water inlet 38 and outlet 39 and having a control value 40. At its upper end, chute 36 is connected to a storage funnel 41 containing a rotating screw mechanism 42. A substrate 43, which is to be coated, is positioned within the vacuum chamber against a water cooled backing 44 provided with water cooling means 45. The water cooled backing is provided with supports 46 which also support water cooling means 45 and substrate 43.

In operation, storage funnel 4i and screw mechanism 42 operate to deliver a pre-alloyed powder 46 through chute 36 by rotating screw mechanism 42 through the use of a motor or other power means, not shown. The alloy powder is moved through the storage funnel to water cooled chute 36 along the threads of the rotating screw. The tip of chute 36 is supported about an inch above crucible 35 which is heated by heating circuit 34. The alloy powder is evaporated by dropping it at a controlled rate through chute 38 into crucible 35 which is controlled at an elevated temperature. The alloy powder particles are evaporated instantaneously as they hit the hot crucible and thus avoid the problem of fractionation which commonly occurs when two or more elements are evaporated simultaneously. The vacuum conditions, water cooling means, substrate materials and temperatures, etc., are substantially the same as those defined in the description of the apparatus of Fig. l.

semiconducting compounds are generally composed of combinations of a metal with a non-metal. ln delineating the boundary between metals and non-metals, the line drawn diagonally through the periodic table, known as the Zintl border, serves to differentiate the metals from the non-metals. In this invention at least one element is taken from each side of this line, with the non-metal being solid at room temperature and the deposited materials being characterized in that they are non-stoichiometric. Although crystalline compound semiconductors may be capable of small deviations from stoichiometry, the vitreous materials of the pres ent invention can have wide deviations on the side of stoichiometry which has excess non-metal. That is, by properly controlling the respective evaporation rates and by holding the substrate at a temperature below the condensation point of either component, and particularly below the condensation point of the non-metal, excess non-metal (i.e. more than a stoichiometric amount) is deposited in a thin semiconductive layer. Prior to this invention vitreous semiconductive materials of this type, especially those having a substantial but less than stoichiometric percentage of metal, could not be prepared.

The structure of the materials of this invention are in the glassy rather than the crystalline state. The structure is characterized by the absence of intermediate or long-range-order. X-ray diffraction patterns are of the so-called vitreous or non-crystalline type. These compounds cannot normally be prepared as glasses (cooled from the melt) and there is no report of vitreous materials or glasses ever having been prepared in these systems. There are, however, reports of unsuccessful attempts to prepare these materials. In particular, Kolomiets et al., The Structure of Glass", Vol. 2, page 4 l 0, Consultants Bureau, New York (I960), could not obtain glasses when either cooper, silver, gold, zinc, cadmium, mercury, gallium, indium, thallium, germanium, tin or lead was heated together with selenium, sulfur, or arsenic at 900C followed by quenching.

With respect to the electrical properties, the vitreous materials of this invention can best be described as semiconductors or semi-insulators, that is, having a valence and conduction band separated by a forbidden energy gap. They possess electronic properties different from those of components taken either alone or combined in a stoichiometric crystalline condition. Although they may be properly described as thermodynamically metastable, they possess a high degree of phenomenological stability and retain their structure well above room temperature. Their crystallization temperature in some instances has been observed to be higher than either component alone.

These vitreous materials may be prepared only by quenching from the vapor phase and not by any of the melt techniques. In fact, many of the materials are immiscible in the liquid state to well above the boiling point of one of the components.

Vitreous semiconductive materials having up to the stoichiometric amount of metal can be produced in accordance with the herein disclosed method. The present invention and the products produced thereby should not be confused with doped vitreous layers, such as doped selenium. In doped layers, the dopants are normally present in extremely minute quantities, on the order of parts per million. Such products can be produced in accordance with well-known melt or diffusion techniques. It was not possible, until the present invention, to include substantial but less than stoichiometric amounts of the metal components without crystallizing the non-metallic component. The present invention, however, achieves such incorporation without undersirable crystallization. As this incorporation forms an essential feature of the present invention, a preferred range of materials includes those semiconductive materials having substantial, but less than a stoichiometric amount, of the metal component. By substantial, it is meant more than doping quantities and at least 0.5 atomic percent metal. In general, such materials cannot be produced with prior art techniques because of phase immiscibility at higher concentrations of the metal component. In accordance with the herein disclosed method, such semiconductive materials can be produced in the amorphous state.

In a typical embodiment of this invention, the nonmetal selenium and a metal from the group consisting of cadmium, zinc, gallium, lead, thallium and bismuth form a family of vitreous semiconductors having particular application to the field of xerography. These compounds show photoconductive spectral response in wavelengths from the visible all the way to and including the infrared. The above metals in combination with selenium form vitreous semiconductors capable of receiving an electrostatic charge, and upon exposure to light, forming an electrostatic latent image, which is capable of being developed in the well-known xerographic mode such as that set forth in Carlson U.S. Pat. No. 2,297,69l, and other related patents in the xerographic field.

Vitreous films formed by combining the metal bismuth with selenium have been found to be sensitive to infrared radiation and may, therefore, be employed in xerographic systems receiving radiation which is out of the visible spectrum. Films of bismuth and selenium also may be employed as the photoconductive layer for use in a vidicon device. In particular, a preferred range for bismuth, on the order of about 0.5 to 4.0 atomic percent (about l.3-l0 wt. percent) in combinatnion with selenium has been shown to have a significant effect in increasing the spectral sensitivity in the infrared region. Amounts of bismuth greater than about 4 percent result in increased conductivity of the vitreous film and make it unsuitable for conventional xerographic purposes or for use in a vidicon, both of which require the retention of the latent electrostatic image on the surface of the bismuth-selenium film.

It has further been discovered, that within the preferred range of about 0.5 to 4.0 atomic percent bismuth with selenium, a critical range of about 0.5 to 2.0 atomic percent (about L3 to 5.1 wt. percent) bismuth yields particularly outstanding results when used for xerographic applications. As shown in FIG. 3, xerographic gain or quantum gain is plotted as a function of wavelength for a series of bismuth-selenium films in a composition range of high sensitivity. The sensitivity of these films is compared to a film of vitreous selenium such as those described by Bixby in U.S. Pat. No. 2,907,906.

For a given field, xerographic gain, G, (quantum gain) is defined by the relationship G=(Ke0/edF) (dv/dt) where K is the dielectric constant of the material. A value of 6.3 was used for pure selenium, while a value of 7.0 was used for all of the bismuth alloys in order to simplify calculations, and because the variation in the amount of bismuth was very small. The permittivity of free space is co, e is the charge on the electron, and d is the film thickness. F is the photon flux as measured with a thermopile and is about 10 photonslcm -sec; and dV/dt is the initial value of the slope of the xerographic discharge curve which is obtained by corona charging the surface of the bismuth-selenium film to a given applied field, exposing the charged surface to a given wavelength and intensity, and measuring the voltage drop as a function of time with a calibrated d.c. electrometer probe. In the xerographic mode the maximum quantum gain is unity (1.0) and is achieved if each incident photon results in the generation of an hole-electron pair which is collected at the electrodes. The curves for the various bismuth-selenium compositions shown in FIG. 3 are obtained by exposing the top surface of a given plate which was positively charged. A five minute interval was allowed between sucessive measurements for recovery from any fatigue effects which manifested themselves as increased dark discharge. For the curves shown in FIG. 3 the initial applied field in each case was approximately 2 X 10" volts/cm. In general, with respect to selenium the short wavelength sensitivity decreases with increasing bismuth content while at longer wavelengths sensitivity is increased by the presence of bismuth. Higher bismuth contents than those shown here, (greater than about 2 atomic percent bismuth) result in extremely high dark decay rates making xerographic measurements difficult. To a certain extent, the preferred range of about 0.5 to 2 atomic percent bismuth (balance selenium) may be increased by the addition of a halogen such as iodine as shown in the curve for 2.0 percent bismuth doped with 4000 parts per million (ppm) iodine. A satisfactory range for the halogen is from about 1000 to 5000 ppm, with iodine being preferred. Concentrations outside this range, however, may also be used.

The samples for five bismuth-selenium alloys shown in FIG. 3 are prepared by the flash evaporating technique described in Example XXVIII. In FIG. 3 the curve for the selenium plate is shown for comparison and contains a 40 micron layer of vitreous selenium on an aluminum substrate formed by conventional vacuum evaporation techniques such as described by U.S. Pat. No. 2,970,906 to Bixby. It can be seen that the bismuth-selenium alloys exhibit longer wavelength sensitivity than conventional vitreous selenium. The quantum or xerographic gain illustrated in FIG. 3 was measured by the technique described above.

An additional range for bismuth within the 0.5 to 4.0 percentage range having preferred utility for a vidicon device has also been discovered. This preferred range is from about 2.0 to 4.0 atomic percent bismuth (balance selenium). In FIG. 4 the vidicon sensitivity is shown for various compositions ranging from about to 4.5 atomic percent bismuth (balance selenium). It can be seen that the percentage range of preferred vidicon sensitivity is from about 2.0 to 4.0, with a range of about 2.5 to 3.5 percent showing maximum sensitivity. in plotting the sensitivity of FIG. 4, a series of plates ranging from about 0 to 4.5 atomic percent bismuth (balance selenium) are formed by the method of Example XVII, using the method of Example I, and apparatus of the type shown in FIG. 1. The bismuth source is maintained at a temperature of about 665C, while the seleniuim source is controlled at a temperature of about 258C. The samples or plates comprise vitreous films of bismuth-selenium ranging in thickness from about 5 to 30 microns contained on a NESA substrate.

in order to measure vidicon sensitivity as shown in FIG. 4, the image of an illuminated target in the form of a bar is focused upon a given bismuth-selenium photoconductor plate in the vidicon. The wavelength of the illumination as well as the target voltage is adjusted for peak signal output. The output signal, as viewed on an oscilloscope, is varied by varying illumination on the target. When the output signal voltage is equal to times the noise voltage, which was previously determined by observing the output signal with the illumination off, a thermopile of known sensitivity is placed exactly where the photoconductor had been during the measurement. The number of watts per square centimetr of light that had been falling on the vidicon target is then determined from the thermopile reading (a thermopile is used to measure light intensity because its output is independent of wavelength which is particularly convenient in the infrared). Since the smaller the number of watts per square centimeter, the higher the sensitivity, the sensitivity is expressed as the reciprocal of the number of watts per square centimeter so determined. Conventional TV scan rates are used during the measurement i.e. 525 lines per picture, 30 frames a second, 4/3 aspect ratio and 2:1 interlace.

The term NEH representing sensitivity in FIG. 4 is the illumination in watts/square cm. as determined by the thermopile. To show the signal to noise ratio was 10 to l we use HEH The reciprocal of this is the sensitivity or NEH with the units being in cmlwatt. From the plot of vidicon sensitivity, it can be seen that for a range of about 2.0 to 4.0 a preferred sensitivity region exists, with optimum or maximum sensitivity occurring in the range of about 2.5 to 3.5 percent bismuth.

Higher percentages of bismuth-selenium can be effectively utilized in systems other than xerographic or vidicon applications which do not require the retention of such a latent electrostatic image. Such systems include infrared photodetection, light amplifier panels, electro-luminescent and other electrical-optical devices. It has been found that bismuth-selenium alloys having a composition range of about 10-18 atomic percent bismuth (about 23-37 wt. percent) have been shown to have the best photodetection response in consdering these non-xerographic or vidicon applications. Accordingly, the forementioned percentage ranges are preferred for this particular semiconductor system when utilized as described above.

It should be noted, however, that the range of about 10-18 percent bismuth could be used in a vidicon or for xerographic use if used in a matrix hinder or in a layered configuration in conjunction with photoconductor materials having higher resistivities than these bismuth-selenium compositions.

When used in a xerographic mode, any of the above suitable materials are evaporated onto a conductive substrate such as brass, aluminum, stainless steel, con ductively coated glass or plastic, etc. The thus formed xerographic plate is then given a uniform electrostatic charge by a corona discharge device in order to sensitize its entire surface. The plate is then exposed to an image of activating electromagnetic radiation, such as light, which selectively dissipates the charge in the illuminated areas of the photoconductor while leaving behind a latent electrostatic image in the non-illuminated areas. This image may be developed and transferred to another material, with development being carried out by depositing finely divided, electroscopic marking particles on the surface of the photoconductive material to make said image visible. It should be pointed out that any suitable method may be used to attain an electrostatic image. Typical techniques are by use of a pin matrix as a print head, pin tubes, etc.

In another embodiemnt of this invention, it is possible to control the degree of order present. Under certain conditions a second phase of intermediate or long range order and crystalline in nature may be obtained dispersed throughout the vitreous non-crystalline matrix. Two critical parameters in achieving this result are (l) the system (i.e., the metal and non-metal) utilized and (2) the substrate temperature. For a given system and a given substrate temperature, a particular concentration of metal in the vitreous matrix will be reached above which crystallinity will appear. To increase the concentration of the metal component in the vitreous matrix without achieving crystallinity, the substrate temperature, for example, can be lowered. On the other hand, to achieve greater crystallinity the substrate temperature can be increased.

As indicated above, for a given system and substrate temperature, a concentration of metal component will be reached above which crystallinity will appear. Accordingly, crystallinity can also be controlled by controlling the relative amounts of the two evaporating species. That is, by providing a percentage of metal greater than the particular value for crystallinity to appear, crystallinity will be achieved within the vitreous non-crystalline matrix. By providing a lower percentage of metal than the particular threshold value, no crystalline material is found dispersed throughout the vitreous matrix. The relative amounts of the two evaporating species can be controlled by varying their respective source temperatures. The second intermediate or long-range order phase may be obtained dispersed in the vitreous non-crystalline matrix by raising the temperature of one of the evaporating components to a relatively higher rate than the other component, the rate being such that it is above the particular threshold value at which crystallinity will begin to appear. For example, a cadminurn-selenium film having approximately 30% of an intermediate or long-range order crystalline phase dispersed in a vitreous matrix of cadmium and selenium is obtained by maintaining the selenium at a evaporation temperature 217C and raising the evaporation temperature of the cadmium to about 375C (from the normal evaporation of about 322C).

Another technique for achieving the same result is by subsequently heat treating the deposited semiconductive layer.

The use to which such vitreous semiconductors may be employed is as varied as the uses to which semiconductors and semi-insulators have been used in the past. These uses include photoconductors; luminscent materials; electroluminescent materials; switching devices; super-conductors; thermoelectric materials; ferroelectric materials; magnetic materials; electrophotographic receptors and many more.

DESCRIPTION OF SPECIFIC EMBODIMENTS The following examples further specifically define the present invention with respect to the method of making and using vitreous semiconductors. The parts and percentages are by weight unless otherwise indicated. The examples below are intended to illustrate the various preferred embodiments of the invention.

EXAMPLE I A 7 micron thick film containing about 20 percent cadmium and 80 percent selenium on a NESA plate is prepared by placing 10 gram samples each of cadmium and selenium pellets into separate quartz crucibles. The quartz crucibles are placed into a vacuum chamber and heat fused to make it permanent Good quality copies of an original are obtained by this method.

EXAMPLE III EXAMPLE IV A film comprising a matrix of vitreous cadmium and selenium containing about percent of an intermediate or long-range-order crystalline phase dispersed throughout said matrix is prepared on the NESA substrate by the method of Example I, by increasing the temperature of said substrate to about 140C.

EXAMPLE V A film comprising a matrix of vitreous cadmium and selenium containing about 30 percent of an intermedi ate or long-range-order crystalline phase dispersed throughout said matrix is prepared on a NESA sub strate by the method of Example I, where subsequent which is evacuated to a vacuum of about 2 X 10 Torr.

A substrate of NESA glass is placed on a water cooled base located about [2 inches above the quartz cruciblesand maintained at a temperature of about 54C. The NESA glass is masked with a thin aluminum plate which is removed from the NESA surface as soon as the cadmium and selenium crucibles reach their evaporation temperature. The cadmium and selenium are then evaporated onto the NESA substrate by maintaining the temperature of the cadmium crucible at about 322C and the selenium crucible at about 217C by means of resistance heating elements. These conditions are maintained for about 2% hours at which time the evaporation is terminated. The vacuum chamber is cooled to room temperature, the vacuum is then broken, and the film coated NESA plate removed from the chamber. No crystallinity is detected in the film when examined by x-ray diffraction. When tested for photoconductive spectral response, it is observed that the photoconductivity edge is extended about 900 angstroms toward longer wavelengths. Also of interest, is the that crystallization temperature as measured by differential thermal analysis is about 20 higher than pure selenium.

EXAMPLE [I The vitreous cadmium-selenium coated plate formed by the method of Example I, is then used as follows in a xerographic mode. The plate is corona charged to a positive potential of about 300 volts, and then exposed to a 100 watt tungsten light source at a distance of about 16 inches for about 2 seconds to form a latent electrostatic image on the surface of said plate. The latent image is then developed by cascading an electroscopic marking material across the surface containing said image. The image is transferred to a sheet of paper to the treatment set forth in Example I, the film and substrate are heated at a temperature of about 120C for about 5 minutes.

EXAMPLE VI A 19 micron thick film containing about 5 percent lead and percent selenium is prepared on a NESA substrate by the method of Example I. During the evaporation, the lead containing crucible is held at a temperature of about 803C while the selenium containing crucible is maintained at about 217C. Evaporation is complete in about 2 hours. X-ray diffraction reveals a vitreous structure with no evidence of crystallinity. The absorptions edge of this material occurs at about 1.1 microns. A peak in photosensitivity is observed at 7000 angstroms, athough at 8000 angstroms the photosensitivity is still about one-third the peak value. Steady state photoconductivity is observed out to the absorption edge (approximately 1.2 microns). The absorption edge and photoconductive edge are far from corresponding edges for either PbSe or selenium. Also, the vitreous lead-selenium material has a conductivity between that of selenium and PbSe. Thus, the electronic properties for the vitreous material are drastically different from the properties of any other components, or crystalline combination of the components.

EXAMPLE VII The plate of Example VI is then charged, exposed, and developed in the xerographic mode of Example II to form a readable copy of an original image.

EXAMPLE VIII A 24 micron film containing about 8 percent zinc and 92 percent selenium on an aluminum substrate is prepared by the method of Example I. During evaporation of the components, the crucible containing the zinc is maintained at a temperature of about 41 1C, while the selenium containing crucible is maintained at about 217C. This film, when tested by x-ray diffraction, exhibits a non-crystalline structure and when tested for photoconductive spectral response, revealed a photoconductivity edge extending about 700 angstroms toward longer wavelengths as compared with vitreous se lenium. The fundamental absorption edge of crystalline ZnSe occurs at 4.700 angstroms and thus crystalline ZnSe could not account for the extended spectral sensitivity.

EXAMPLE D4 The plate of Example VIII is then charged, exposed, and developed in the xerographic mode of Example II to form a readable copy of an original image.

EXAMPLE X A film containing about 25 percent cadmium and 75 percent selenium is prepared by the method set forth in Example I. During the evaporation step the cadmium containing crucible is maintained at a temperature of 356C and the selenium at 217C. X-ray diffraction reveals a vitreous structure.

EXAMPLE X] A film coating about percent Zn and 90 percent selenium is prepared by the method set forth in Example l. The zinc containing crucible is maintained at a temperature of about 385C while the selenium is maintained at about 217C. No crystallinity is detected when this film is examined by x-ray diffraction.

EXAMPLE XII A film containing about 1.5 percent bismuth and 98.5 percent selenium is prepared by the method set forth in Example I. The crucible containing bismuth is maintained at a temperature of about 751C while the selenium is maintained at a temperature of about 217C. The resulting vitreous film is then used as a xerographic infrared photoreceptor by subjecting the plate to the steps of charging, exposing and developing by the method of Example II. Successful images are made using filters which cut out all visible light and transmit only radiation of wavelength greater than 8200 angstroms.

EXAMPLES XII] A film containing about 20 percent bismuth and 80 percent phosphorous is prepared by the method of Example I. The crucible containing the bismuth is maintained at a temperature of about 751C while the crucible containing phosphorous is maintained at about 187C. This film shows a vitreous structure when examined by x-ray diffraction.

EXAMPLE XIV A film containing about percent zinc and 85 percent boron is prepared by the method of Example I. The crucible containing the zinc is maintained at a temperature of about 385C while the boron containing crucible is maintained at a temperature of about 2100C by evaporating the boron with an electron gun. No evidence of crystallinity is detected when examined by x-ray diffraction.

EXAMPLE XV A film containing about 25 percent cadmium and 75 percent sulfur is prepared by the method set forth in Example I. The crucible containing the cadmium is maintained at a temperature of about 356C while the crucible containing sulfur is maintained at a temperature of about 100C. When tested by x-ray diffraction the film reveals a vitreous structure.

EXAMPLE XVI A film containing about 10 percent zinc and percent sulfur is prepared by the method as set forth in Example l. The crucible containing the zinc is maintained at a temperature of about 385C while the crucible containing the sulfur is maintained at a temperature of about C. No evidence of crystallinity is detected when this film is examined by x-ray diffraction.

EXAMPLE XVII A 17.1 micron amorphous film containing about 3 percent bismuth and 97 percent selenium is prepared by the method as set forth in Example I. The crucible containing the bismuth is maintained at a temperature of about 665C while the crucible containing the selenium is maintained at a temperature of about 326C. The substrate is maintained at about 52C.

EXAMPLE XVIII A 62 micron amorphous film containing about 4.5 percent bismuth and 95.5 percent selenium is prepared by a modified form of the method as set forth in Example I. The bismuth is evaporated from a Knusden source held at a temperature of about 756C while the crucible containing the selenium is maintained at a temperature of about 239C. The substrate is held at a temperature of about 52C.

EXAMPLE XIX A 25 micron amorphous film containing about 6.4 percent bismuth and 93.6 percent selenium is prepared by the method as set forth in Example I. The bismuth source is held at about 680C while the selenium source is held at about 290C.

Examples XVII XIX have resistivities on the order of 10 10" ohm-centimeters, the resistivities decreasing with increasing bismuth percentage. As these films are sensitive to near (on the order of about 1 micron) infrared radiation, this combination of properties makes the materials suitable for near infrared xero graphic photoreceptors.

EXAMPLE XX A 12 micron amorphous film containaing about 25 percent bismuth and about 75 percent selenium is prepared by the method as set forth in Example I. The bismuth source is held at about 744C while the selenium source is maintained at about 242C.

EXAMPLE XXI A 16 micron amorphous film containing about 30 percent bismuth and about 70 percent selenium is prepared by the method as set forth in Example I. The bismuth source is held at about 719C while the selenium source is held at 250C. This film is found to have resistivity on the order of 10" ohm-centimeters and represents the approximate maximum photosensitivity for the vitreous bismuth-selenium semiconductors deposited on substrates held at about 5055C. While the resistivity of this material is on the low side for xerographic applications, the photosensitivity characteristics of this material make it exceptionally useful for near infrared photodetection apparatus.

EXAMPLE XXII A 13 micron amorphous film containing about 33 percent bismuth and about 67 percent selenium is prepared by the method as set forth in Example I. The bismuth source is held at about 726C while the selenium source is held at a temperature of about 258C. The substrate is held at about 55C.

EXAMPLE XXIII A 32 micron amorphous film containing about 36 percent bismuth and about 64 percent sleneium is prepared by a method as set forth in Example I. The bismuth source is held at about 790C while the selenium source is held at about 242C. The substrate is held at about 53C.

EXAMPLE XXIV A 29.2 micron amorphous film containing about 15.6 percent gallium and about 84.4 percent selenium is prepared by the method as set forth in Example I. The gallium source is maintained at about 1087C while the selenium source is maintained at about 217C. The substrate temperature is maintained at about 53C.

EXAMPLE XXV A 20 micron thick film containing about 7.8 percent thallium and about 92.2 percent selenium is prepared by the method as set forth in Example 1. The thallium sources is maintained at about 780C while the selenium source is maintained at about 217C. X-ray examination indicates some crystallization of the selenium.

EXAMPLE XXVI An 8.9 micron amorphous film containing greater than percent but less than 50 percent indium, the balance being arsenic is prepared by the method set forth in Example I. The indium source is held at a temperature of about 990C while the arsenic source is maintained at about 390C. The substrate is held at a temperature of about 25C.

EXAMPLE XXVII A thin film containing about 10 percent antimony and about 90 percent arsenic is prepared by the method as set forth in Example I. The antimony source is maintained at about 518C while the arsenic source is maintained at about 290C. The substrate is held at a temperature of l96C.

EXAMPLE XXVIII 700C for 24 hours in a furnace. Mechanical mixing is promoted by rocking the furnace. The ampoules were water quenched, opened, and the contents ground to a powder. Particle sizes of about 100 to 1000 microns were selected for use in the evaporation. It should be noted that the 2.0 atomic percent bismuth alloy was additionally doped with about 4000 ppm iodine.

Each of the five films were then formed by flash evaporation by the following technique. The alloy powder is loaded in the storage funnel of the apparatus shown in FIG. 2. A screw mechanism is designed for the controlled delivery of the powder from the storage funnel to a water cooled chute along the threads of a rotating screw. The lower end of the chute is disposed about 1 inch above a quartz crucible surrounded by heating coils. The alloy powder is evaporated by dropping it at a controlled rate from the chute into the crucible which is held at an elevated temperature of about 500-600C. Because of the relatively high vapor pressure of both bismuth and selenium at these temperatures, the particles evaporate instantaneously as they strike the hot crucible. The evaporated vapor is condensed in the form of vitreous film of bismuth-selenium on the surface of a water cooled aluminum substrate supported above the crucible. The substrate temperature is controlled at about 50C. The pressure in the vacuum chamber is maintained at about 10 Torr with deposition taking place at the rate of about 4 microns per hour.

Although specific components and proportions have been stated in the above description of the specific embodiments of this invention, other suitable materials and procedures, such as those listed above, may be used with similar results. For example. a bismuthselenium film having a composition gradient throughout the film thickness may be employed for use in a vidicon. In such an embodiment, the bismuth and selenium could be evaporated from a dual source, such as illustrated in FIG. 1, to form a film having a relatively large amount of bismuth at the substrate, with progressively lesser amounts of bismuth through the film thickness toward the outer surface, which would have the least amount of bismuth. In addition, other materials may be added which synergize, enhance or otherwise modify the properties of the plates.

Other modifications and ramifications of the present invention would appear to those skilled in the art upon reading the disclosure. These are intended to be included within the scope of this invention.

What is claimed is:

1. A photosensitive element exhibiting infrared sensitivity and adapted for use in a vidicon device, said element comprising an electrically conductive supporting substrate having thereon a vitreous bismuth-selenium film which comprises about 2.0 to 4.0 atomic percent bismuth with the balance comprising selenium.

2. The element of claim 1 in which the bismuth comprises about 2.5 to 3.5 atomic percent.

Claims

1. A PHOTOSENSITIVE ELEMENT EXHIBITING INFRARED SENSITIVITY AND ADAPTED FOR USE IN A VIDCON DEVICE, SAID ELEMENT COMPRISING AN ELECTRICALLY CONDUCTIVE SUPPORTING SUBSTRATE HAVING THEREON A VITREOUS BISMUTH-SELENIUM FILM WHICH COMPRISES ABOUT 2.0 TO 4.0 ATOMIC PERCENT BISMUTH WITH THE BALANCE COMPRISING SELENIUM.